Hair cosmetic compositions

ABSTRACT

A liquid hair cosmetic composition comprising: 
     (A) From about 0.1% by weight to about 10% by weight (acid basis) of a silicone-containing polycarboxylic acid copolymer having a vinyl polymeric backbone, and having grafted to the backbone a silicone-containing macromer having a weight average molecular weight of from about 1,000 to about 50,000. (B) A neutralizing system consisting essentially of sodium hydroxide present at a lever sufficient to neutralize at least about 25% of the acid groups on the silicone containing copolymer; (C) From about 0%-1.0% by weight of water; and (D) The balance comprising a carrier suitable for application to hair. The liquid hair cosmetic products have improved clarity and storage stability and demonstrate excellent hair styling benefits in addition to hair feel attributes and ease of removal and brush out.

TECHINCAL FIELD

The present invention relates to hair cosmetic compositions. Moreparticularly, this invention relates to liquid hair cosmeticcompositions containing silicone-grafted hair styling polymers havingimproved long term product stability, hair feel attributes and ease ofremoval and brush out as well as excellent style retention properties.

BACKGROUND OF THE INVENTION

The desire to have the hair retain a particular shape is widely held. Acommon methodology for accomplishing this is applying hair styling, or"setting" compositions to the hair, typically to damp or dry hair. Thesecompositions provide temporary setting benefits, and should be removableby water and/or by shampooing. The materials used in the compositions toprovide the setting benefits are generally applied in the form ofmousses, gels, lotions or sprays.

High levels of style retention, or hold, are typically expected fromhair styling compositions applied as a spray. Style retention istypically achieved by the use of resins, such as AMPHOMER, supplied byNational Starch, and GANTREZ SP 225, supplied by GAF. As used incommercially sold hairspray products, these resins generally have aweight average molecular weight of from about 40,000 to about 150,000.

When such resins are incorporated into pump and aerosol hairsprays, theycan provide suitable style retention attributes. However, such resinsare found to be deficient in the area of hair feel and can give a stiffhair feel.

Recently, it has been found that certain neutralisable polymers havingsilicone macromer portions can provide good style retention benefits tothe hair while also providing improved hair feel. In other words, suchsilicone macromer-containing polymers can impart a tactile sense ofsoftness and conditioning to the hair relative to conventional,non-silicone-containing resins without the tacky hair feel traditionallyassociated with non-silicone hair fixative polymers. Siliconemacromer-containing hair styling polymers and formulations containingthem are disclosed, for example, in EP-A-0,408,311 A2 issued Jan. 11th1991, Hayama, et al., U.S. Pat. No.5,061,481, issued Oct. 29th 1991,Suzuki et al., U.S. Pat. No.5,106,609, Bolich et al., issued Apr. 21st1992, U.S. Pat. No. 5,100,658, Bolich et al., issued Mar. 31st 1992,U.S. Pat. No. 5,100,657, Ansher-Jackson, et al., issued Mar. 31st 1992and U.S. Pat. No. 5,104,646, Bolich et al., issued Apr. 14th 1992.

It is well known that at least partial neutralisation of the siliconemacromer-containing hair styling polymer is necessary to maximise itsutility in hair styling compositions. Typically, silicone graftedco-polymers neutralised with potassium hydroxide exhibit good solubilityin hairspray compositions containing 15% water. However, potassiumhydroxide neutralised systems are less soluble in compositions whichcontain lower levels of water and lead to hazy, colloidal systems.Moreover, silicone grafted co-polymers which are neutralised withorganic neutralisers are found to lead to a somewhat tacky hair feel andare not easily removed from the hair by washing or brush-out.

Thus a need exists for hair styling compositions which have a clearappearance, deliver effective style retention, impart a hairconditioning effect, have a non-sticky hair feel, are easily brushed outand at the same time have stable product and viscosity characteristicsand remain fully stable under long term and stressed temperaturestorage.

SUMMARY OF THE INVENTION

According to one aspect of the invention, there is provided a liquidhair cosmetic composition comprising:

(a) from about 0.1% by weight to about 10% by weight (acid basis) of asilicone-containing polycarboxylic acid copolymer having a vinylpolymeric backbone, and having grafted to the backbone asilicone-contaning macromer having a weight average molecular weight offrom about 1,000 to about 50,000;

(b) a neutralising system consisting essentially of sodium hydroxidepresent at a level sufficient to neutralise at least about 25% of theacid groups on the silicone-containing copolymer;

(c) from 0% to about 1.0% by weight of water; and

(d) the balance comprising a carrier suitable for application to hair.

The essential, as well as the optional, components of the presentinvention are described below. All levels and ratios are on a weightbasis unless otherwise specified.

The compositions of the present invention contain from about 0.1% toabout 10.0%, preferably from about 0.5% to about 8.0% and especiallyfrom about 1% to about 6% of specifically defined silicone-containingcopolymers. It is these polymers which provide the unique hairconditioning and hair setting characteristics of the present invention.The polymers preferably have a weight average molecular weight of fromabout 10,000 to about 1,000,000, preferably from about 30,000 to about300,000, most preferably from about 90,000 to about 300,000 and,preferably, have a Tg of at least about -20° C. As used herein, theabbreviation "Tg" refers to the glass transition temperature of thenon-silicone backbone, and the abbreviation "Tm" refers to thecrystalline melting point of the non-silicone backbone, if such atransition exists for a given polymer.

The molecular weights and molecular weight distributions of the polymersutilised in the compositions according to the present invention aredetermined by Size Exclusion Chromatography (SEC). In practise, polymerscomprise a distribution of molecular weight species that gives rise totheir unique properties. Separation of the molecules is accomplished bySize Exclusion Chromatography (SEC) using a crosslinkedpolystyrene-divinylbenzene column (MW range =100-10⁷) with adifferential refractive index detector and a differential viscometer. Auniversal calibrationn curve is prepared from monodispersed polystyrenestandards of known molecular weight (MW) and molecular weightdistribution (MWD). MW and MWD of the given polymer are determined basedon concentration and viscosity responses relative to the calibration.

Preferred polymers comprise a vinyl polymeric backbone, preferablyhaving a Tg above about -20° C. and, grafted to the backbone, asilicone-containing macromer having a weight average molecular weight offrom about 1,000 to about 50,000, preferably from about 5,000 to about40,000, most preferably from about 10,000 to about 20,000. The polymeris such that when it is formulated into the finished hair carecomposition, when dried, the polymer phase separates into adiscontinuous phase which includes the silicone containing macromer anda continuous phase which includes the backbone. It is believed that thisphase separation property provides a specific orientation of the polymeron hair which results in the desired hair conditioning and settingbenefits.

In its broadest aspect, the copolymers utilized in the presentapplication comprise a silicone-containing monomer (hereafter identifiedas C) together with a hydrophilic carboxylate-containing monomer (B) andoptionally a lipophilic monomer (A).

Examples of useful copolymers and their preparation are described indetail in U.S. Pat. No.4,693,935, Mazurek, issued Sep. 15th 1987, andU.S. Pat. No.4,728,571, Clemens et al., issued Mar. 1st 1988. Thesecopolymers comprise monomers A,B and C as defined above. In preferredembodiments, A comprises at least one free radically polymerizable vinylmonomer or monomers and B comprises at least one reinforcing monomercopolymerizable with A and selected from the group consisting ofcarboxylate-containing monomers and macromers having a Tg or a Tm aboveabout -20° C. B can be up to about 98%, preferably up to about 80%, morepreferably up to about 30%, of the total monomers in the copolymer.Monomer C comprises from about 0.1% to about 50.0% of the total monomersin the copolymer.

Representative examples of A (hydrophobic) monomers are the acrylic ormethacrylic acid esters of C₁ -C₁₈ alcohols, such as methanol, ethanol,methoxy ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol,1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol,1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-i-pentanol,2-methyl-1-pentanol, 3-methyl-1-pentanol, t-butanol(2-methyl-1-propanol), cyclohexanol, neodecanol, 2-ethyl-1-butanol,3-heptanol, benzyl alcohol, 2-octanol, 6 methyl-1-heptanol,2-ethyl-1-hexanol, 3.5-dimethyl-1-hexanol, 3,5,5-tri-methyl-1-hexanol,1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol, and the like, thealcohols having from about 1-18 carbon atoms with the average number ofcarbon atoms being from about 4-12; styrene; polystyrene macromer; vinylacetate; vinyl chloride; vinylidene chloride; vinyl propionate;alpha-methylstyrene; t-butylstyrene; butadiene; cyclohexadiene;ethylene; propylene; vinyl toluene; and mixtures thereof. Preferred Amonomers include n-butyl methacrylate, isobutyl methacrylate,2-ethylhexyl methacrylate, methyl methacrylate, t-butylacrylate,t-butylmethacrylate, and mixtures thereof.

Representative examples of B (hydrophilic) neutralisable monomerscontaining a carboxyl moiety include acrylic acid, methacrylic acid,maleic acid, maleic anhydride, half esters of maleic anhydride, crotonicacid, and itaconic acid. Preferred B monomers include acrylic acid andmethacrylic acid and mixtures thereof.

The C monomer preferably has the general formula (I):

    X (Y).sub.n Si(R).sub.3-m Z.sub.m                          (I)

wherein X is a vinyl group copolymerizable with the A and B monomers; Yis a divalent linking group; R is hydrogen, C₁ -C₄ alkyl, aryl, alkylamino, tri(C₁ -C₄ alkyl)siloxy or C₁ -C₄ alkoxy; Z is a monovalentsiloxane polymeric moiety; n is 0 or 1; and m is an integer from 1 to 3.C has a number average molecular weight of, at least 500, preferablyfrom 1,000 to 50,000. Preferably, the C monomer is selected from one ormore monomers having the general formulae (II to VII): ##STR1## In thesestructures, m is 1,2 or 3 (preferably m=1); p is 0 or 1; R" is a;lyl orhydrogen; q is an interger from 2 to 6; X is ##STR2## R¹ is hydrogen or--COOH (preferably R¹ is hydrogen); R² is hydrogen, methyl or --CH₂ COOH(preferably R² is methyl); Z is ##STR3## R⁴ is alkyl, alkoxy,alkylamino, arly, or hydroxyl (preferably R⁴ is alkyl); and r is aninteger from 5 to 700,preferably from 50 to 500, more preferably from150 to 300. Of the above, formula II is preferred, particularly when p=0and q=3.

The polymers utilized herein generally comprise from 0% to about 98%(preferably from about 5% to about 92%, more preferably from about 50%to about 90%) of monomer A, from about 1% to about 98% (preferably fromabout 7.5% to about 80%) of monomer B, and from about 0.1% to about 50%(preferably from about 0.5% to about 40%, most preferably from about 2%to about 25%) of monomer C. The combination of the A and B monomerspreferably comprises from about 50.0% to about 99.9% (more preferablyabout 60% to about 99.5%, most preferably from about 75% to about 98%)of the polymer.

Preferred silicone-containing copolymers for use herein are selectedfrom:

acrylic acid/n-butylmethacrylate/polydimethylsiloxane (PDMS)macromer--20,000 molecular weight (mw) (10/70/20 w/w/w)

acrylic acid/isobutyl methacrylate/PDMS macromer--20,000 mw (20/60/20w/w/w)

acrylic acid/PDMS macromer--20,000 mw (80/20 w/w)

t-butylacrylate(tBA)/acrylic acid(AA)/PDMS macromer--10,000 mw(60/20/20)

acrylic acid/isobutyl methacrylate/PDMS macromer--20,000 mw (10/70/20);

acrylic acid/methyl methacrylate/PDMS macromer--20,000 mw (40/40/20);

acrylic acid/isopropyl methacrylate/PDMS macromer--20,000 mw (25/65/15);

acrylic acid/methoxyethyl methacrylate/PDMS macromer 20,000 mw(60/25/15);

acrylic acid/PDMS macromer--20,000 mw (80/20); and mixtures thereof.

The silicone-containing copolymers described above can be synthesized byfree radical polymerization of silicone- or polysiloxane-containingmonomers with non-silicone- or non-polysiloxane-containing monomers. Thegeneral principles of free radical polymerization methods are wellunderstood. See, for example, Odian, "Principles of Polymerization", 2ndedition, John Wiley & Sons, 1981, pp. 179-318.

In compositions according to the invention it can be desirable to purifythe silicone containing copolymer by removing unreactedsilicone-containing monomer and silicone macromer-grafted polymer withviscosities at 25° C. of about 10,000,000 centistokes and less. This canbe done, for example, by hexane extraction. After drying the resin fromits reaction solvent, hexane extraction of the reaction product can beperformed by adding an excess of hexane to the reaction product andheating to near the Tg of the non-silicone portion of the polymer. Themixture is held at this temperature with stirring for about 30 minutesand cooled to room temperature. The hexane is removed by vacuum suction.Two more hexane extraction cycles are preferably conducted in the samemanner as above. After the third cycle, residual hexane remaining withthe product is removed by distillation and vacuum drying.

Low molecular weight polysiloxane-containing monomer and polymer issolubilized by supercritical carbon dioxide and transported away fromthe remaining polymer via a transfer line, which is maintained atidentical temperature and pressure as the extraction vessel. Theextracted materials are collected in an extraction vessel. Followingextraction, the system is depressurised and dry, extracted polymer isrecovered from the extraction vessel.

The hair styling polymers herein are utilised in at least partiallyneutralised form in order to aid shampoo removability of the liquid haircosmetic compositions. The present development relates to theneutralisation of a hair fixative polymer (eg silicone grafted tBA/AAcopolymer) with a neutralisation system consisting essentially of aspecific inorganic base, namely sodium hydroxide, in anhydrous oressentially anhydrous aerosol and non-aerosol hairsprays and other haircosmetic products. In particular the present development relates toimproving the clarity, long term storage stability, hair feel attributesand ease of removal characteristics of hairspray and other hair cosmeticproducts containing no or very low levels of water, approximately 0-1%,preferably 0-0.7% water, by neutralisation of the hair fixative polymerwith a neutralisation system comprising at least 80%, preferably atleast 95% and more preferably at least 99% by weight of theneutralisation system of sodium hydroxide. While the neutralisationsystem can be used in excess of the polymer (for example up to 15%excess on an equivalent basis) so as to result effectively in 100%neutralisation of the polymer, nevertheless in preferred compositions, atotal of from about 25% to about 95%, preferably from about 40% to about90%, more preferably from about 55% to about 85%, and especially fromabout 65% to about 80% of the acidic monomers of the polymer areneutralised.

The amount in grams of inorganic base (Z) required to neutralise apolymer can be deduced from calculations which take into account theacid value of the polymer (A); amount of polymer (W); mol wt of the base(B);,mol wt of the acidic moiety (M) and the degree of neutralisationrequired (N).

    Z(g)=W×A/100×1/M×B×N %

In the following example the amount of NaOH required to neutralise 2.6 gof acrylic acid co-polymer (with acid value of 20) to a level of 77%neutralisation is calculated.

    Z(g)=2.6×20/100×1/72×40×0.77

    Z=0.222 g

Note the acid value can be experimentally determined by titrating aspecific amount of the polymer with base or theoretically by consideringthe original acidic content of the co-polymer i.e. a polymer with 20% ofacid monomer has an acid value of 20.

As described earlier herein, use of the herein defined neutralisingsystem for at least partial neutralisation of the silicone graftedcopolymer leads to anhydrous or essentially anhydrous liquid haircosmetic compositions of improved clarity and long term storagestability. Product clarity can be measured using a visible rangespectrophotometer. Using this equipment the percent transmittance of thesample at 450 nm is measured by calibration against a reference sampleof Ethanol B100 as 100% transmittance. Typical transmittance values foropaque systems neutralised with potassium hydroxide neutraliser can beas low as from 1 to 5%. In contrast, the compositions of the inventiontypically display percent transmittance values greater than 80% whenfirst made, preferred compositions herein displaying 80% transmittancevalues after storage for at least four weeks at 45 C.

The liquid hair cosmetic compositions of the present invention alsoinclude a carrier. This can comprise any of those conventionally used inresin hairspray formulations inclusive of solvents, propellants andother optional ingredients of liquid hair cosmetics. The carrier isgenerally present in the liquid hair cosmetic compositions at from about70% to about 99.8%, preferably from about 78% to about 99% by weight.More preferably, the carrier is present at from about 80% to about 98%by weight of the total composition.

Organic solvents suitable for use in the carrier of the presentcompositions include C₁ -C₆ alkanols and ethers, carbitol, acetone andmixtures thereof. C₁ -C₆ alkanols preferred for use in the presentcompositions are C₂ -C₄ monohydric alcohols such as ethanol, isopropanoland mixtures thereof. Dimethoxymethane is also a highly preferredsolvent.

The performance of the liquid hair cosmetic compositions according tothe invention can be improved through the optional incorporation of anonvolatile plasticizer into the composition. The plasticizer willgenerally be present in the compositions at up to a level of 25%,preferable from 1% to 20%, more preferably from 1% to 15%. As usedherein, "nonvolatile" in regard to plasticizers means that theplasticizer exhibits essentially no vapour pressure at atmosphericpressure and 25° C. The polymer-liquid vehicle solution should notsuffer from substantial plasticizer weight loss while the hair cosmeticcarrier is evaporating, since this may excessively reduce plasticizationof the polymer during use. The plasticizers for use herein shouldgenerally have boiling points of about 250° C. or higher.

Plasticizers are well known in the art and are generally described inKirk-Othmer Encyclopedia of Chemical Technology, second edition, Volume15, pp. 720-789 (John Wiley & Sons, Inc. New York, 1968) under the topicheading "Plasticizers", and by J. Kern Sears and J. R. Darby in the textThe Technology of Plasticizers (John Wiley & Sons, Inc., New York,1982). See especially in the Appendix of Sears/Darby Table A. 9 at pages983-1063 where a wide variety of plasticizers are disclosed.

Plasticizers suitable for use in compositions of the present inventioninclude both cyclic and acyclic nonvolatile materials. Suitablecategories of nonvolatile plasticizers include adipates, phthalates,isophthalates, azelates, stearates, citrates, trimellitates, siliconecopolyols, iso C₁₄ -C₂₂ alcohols, methyl alkyl silicones, carbonates,sebacates, isobutyrates, oleates, phosphates, myristates, ricinoleates,pelargonates, valerates, camphor, glycols, amine derivatives, selectedshort chain alcohols and castor oil.

Particularily preferred plasticizers for use herein include glycol andcitrate based plasticizers such as propylene glycol, dipropylene glycol,acetyl tri-n-butyl citrate, triethylcitrate, tri-n-butyl and acetyltri-2-ethoxyhexyl citrate (as supplied by Pfizer under the trade nameCitroflex (RTM) and also glycerin, amino methyl propanol (AMP),diisobutyladipate (DIBA) and isopropanol.

The present compositions can be formulated as hairsprays in aerosol ornon-aerosol forms. If an aerosol hairspray is desired, a propellant mustbe included in the composition. This agent is responsible for expellingthe other materials from the container and forming the hairspraycharacter.

The propellant gas can be any liquefiable gas conventionally used foraerosol containers. Preferably the density of the propellant or mixturethereof is less than 1 so that pure propellant is not emitted from thecontainer. Examples of materials that are suitable for use aspropellants are trichlorofluoromethane, dichlorodifluoromethane,dichlorotetrafluoroethane, monochlorodifluoromethane,trichlorotrifluorethane, dimethylether e.g Dimel 152A (RTM) supplied byDu Pont, propane, n-butane, isobutane, used singly or admixed andpropane butane e.g CAP 80 (RTM). Dimel 152A (RTM) and propane butane arepreferred.

The amount of the propellant gas is governed by normal factors wellknown in the aerosol art. For hairsprays the level of propellant isgenerally from about 10% to about 40%, preferably from about 20% toabout 30%, of the total composition. If a propellant such asdimethylether utilizes vapor pressure suppressant (e.g., trichloroethaneor dichloromethane) the amount of suppressant is included as part of thepropellant.

The hair spray compositions of the present invention can be made usingconventional formulation and mixing techniques. Compositions of thepresent invention can be made by adding the polymer to ethanol andmixing for several hours until dissolved. Plasticizer and neutralisingingredients are then added and the resulting solution is stirred. Anyremaining ingredients such as water, ethanol and perfume can then beadded.

Methods of making the hair cosmetic compositions of the presentinvention are described more specifically in the examples.

Alternatively, pressurised aerosol dispensers can be used where thepropellant is separated from contact with the hairspray composition byuse of specialised containers such as a two compartment can of the typesold under the tradename SEPRO from Americal National Can Corp.

Other suitable aerosol dispensers are those characterized by thepropellant being compressed air which can be filled into the dispenserby means of a pump or equivalent device prior to use. Such dispensersare described in U.S. Pat. No.4,077,441, Mar. 7th 1978, Olofsson andU.S. Pat. No. 4,850,577, Jul. 25th 1989, TerStege. Compressed airaerosol containers suitable for use are also currently marketed by TheProcter & Gamble Company under their tradename VIDAL SASSOON AIRSPRAY(RTM) hairsprays.

Conventional non-aerosol pump spray dispensers, i.e., atomizers, canalso be used.

The liquid hair cosmetic compositions of the present invention can alsocontain a variety of non-essential, optional components such aspreservatives, surfactants, block polymers, thickeners and viscositymodifiers, electrolytes, fatty alcohols, pH adjusting agents, spreadingagents, perfume oils, perfume solubilizing agents, sequestering agents;emollients; lubricants and penetrants such as various lanolincomponents; protein hydrolysates and other protein derivatives; ethyleneadducts and polyoxyethylene cholesterol; sunscreens and volatile andnon-volatile silicone fluids. Such conventional optional ingredients arewell known to a person skilled in the art, e.g. surfactants such asanionics (e.g., sodium alkyl sulphates, nonionics (amine oxides);amphoterics (aliphatic secondary or tertiary amine derivatives)zwitterionics (aliphatic quaternary ammonium; phosphonium or sulphoniumderivatives) and fluorinated surfactants (e.g. Zonyl FSK) (RTM);thickeners and viscosity modifiers such as diethanolamides of long chainfatty acids; block polymers of ethylene oxide and propylene oxide suchas Pluronic (RTM) F88 offered by BASF Wyandotte; fatty alcohols such ascetearyl alcohol; viscosity modifiers such as sodium chloride, sodiumsulphate, and ethyl alcohol; electrolyte such as earth andalkaline-earth metal salts; quaternary ammonium ions and cationic aminesand halogen ions; pH adjusting agents such as citric acid, succinicacid, sodium hydroxide and triethanolamine; spreading agents such asisododecane, perfume oils such as Florasynth (RTM) perfumes; perfume oilsolubilizers such as polyethylene glycol fatty acid esters andsequestering agents such as ethylenediamine tetraacetic acid. Each ofthese optional materials can be present at a level of from about 0.05%to about 5%, preferably from about 0.1% to about 3% by weight ofcomposition.

The liquid hair cosmetic compositions of the present invention are usedin conventional ways to provide the hair styling/holding benefits of thepresent invention. Such method generally involves spraying an effectiveamount of the product to dry or damp hair before or after the hair isstyled, or both. By "effective amount" is meant an amount sufficient toprovide the hair volume and style benefits desired considering thelength and texture of the hair.

The invention is illustrated by the following non-limiting examples.

In the examples, all concentrations are on a 100% active basis, unlessotherwise stated and the abbreviations have the following designation:

    ______________________________________                                        Hair Styling Polymer                                                                       60% t-butyl acrylate/20% acrylic acid/20%                                     silicone PDMS. Weight average molecular                                       weight (measured by SEC) of 150,000.                             NaOH         Sodium hydroxide solution, containing 45%                                     sodium hydroxide and 55% water.                                  Solvent      Ethanol                                                          ______________________________________                                    

EXAMPLES I-VI

The following are liquid hair cosmetic compositions in the form ofhairspray compositions suitable for pump spray dispensers and which arerepresentative of the present invention:

    ______________________________________                                                    I    II     III    IV    V    VI                                  ______________________________________                                        Hair Styling Polymer                                                                        3.0    2.0    4.0  6.0   2.0  5.0                               % poly NaOH neutralised                                                                     82     70     75   80    85   75                                Balance       to 100 percent with ethanol                                     ______________________________________                                    

The balance contains ethanol and optional ingredients such asplasticizer (preferably DIBA), perfume and surfactants.

The hairspray formulations are prepared by adding the polymer directlyto the ethanol. A magnetic or air driven stirrer is used to mix theingredients until the polymer is dissolved, typically about 1 to 2hours. The neutralizing agent is then added and mixed into the premix.Then, the optional ingredients, as may be applicable, are mixed into thecomposition.

The above compositions provide effective style retention, deliver a hairconditioning effect and have excellent long term clarity and a non-tackyhair feel.

EXAMPLES VII-XII

The following are liquid hair cosmetic compositions in the form ofhairspray concentrate compositions suitable for aerosol dispensers andwhich are representative of the present invention:

    ______________________________________                                                    VII  VIII   IX     X     XI   XII                                 ______________________________________                                        Hair Styling Polymer                                                                        4.0    2.0    5.0  6.0   3.0  7.0                               % poly NaOH neutralised                                                                     70     78     85   78    80   75                                Balance       to 100 percent with solvent                                     ______________________________________                                    

As in examples I to VI the balance is ethanol and optional ingredientssuch as plasticizer (preferably DIBA), perfume and surfactants. Theabove compositions are prepared as in Examples I-VI. The concentratesare packaged in conventional aerosol spray cans and are charged with aconventional liquifiable propellant such as CAP 80 (RTM) at apropellant: concentrate weight ratio of 23:77.

The above compositions have excellent clarity and stabilizingcharacterisitcs and when applied to the hair, provide good hair stylingand conditioning benefits as well as a non-tacky hair feel and improvedease of removal.

What is claimed is:
 1. A liquid hair cosmetic composition comprising:a)from about 0.1% by weight to about 10% by weight (acid basis) of asilicone-containing polycarboxylic acid hair styling copolymer having avinyl polymeric backbone, and having grafted to the backbone asilicone-containg macromer having a weight average molecular weight offrom about 1,000 to about 50,000; b) a neutralising system consistingessentially of sodium hydroxide present at a level sufficient toneutralise at least about 25% of the acid groups on thesilicone-containing copolymer; c) from 0% to about 1% by weight ofwater; and d) a carrier suitable for application to hair wherein thecarrier comprises an organic solvent for the silicone-containingcopolymer consisting essentially of C₁ -C₆ alkanols, C₁ -C₆ ethers,carbitol, acetone, or a mixture thereof.
 2. A liquid hair cosmeticcomposition according to claim 1 wherein the silicone-containingmacromer has the general formula (I):

    X(Y).sub.n Si(R).sub.3-m Z.sub.m,                          (I)

wherein X is a vinyl group; Y is a divalent linking group; R ishydrogen, alkyl, aryl, alkylamino, trialkylsiloxy or alkoxy; Z is amonovalent siloxane polymeric moiety having a number average molecularweight of at least about 500; n is 0 or 1; and m is an integer from 1 to3.
 3. A liquid hair cosmetic composition claim 2 wherein thesilicone-containing copolymer has a weight average molecular weight offrom 10,000 to 1,000,000 comprising a hydrophilic carboxylate containingmonomer (B), optionally a lipophilic, low polarity, free-radicallypolymerizable vinyl monomer (A) which is copolymerizable with B, and asilicone-containing macromer (C) having a weight average molecularweight of from 1,000 to 50,000, based on polydimethylsiloxane andwherein the macromer (C) is selected from one or more monomers havingthe general formulae (II-VII): ##STR4## wherein m is 1, 2 or 3; p is 0or 1; R" is alkyl or hydrogen; q is an integer from 2 to 6; X is##STR5## R¹ is hydrogen or --COOH; R² is hydrogen, methyl or --CH₂ COOH;Z is ##STR6## R⁴ is alkyl, alkoxy, alkylamino, aryl or hydroxyl; and ris an integer from 5 to 700; and wherein the silicone-containingcopolymer comprises from 0% to 98% monomer A, from 1% to 98% monomer B,and from 0.1% to 50% monomer C.
 4. A liquid hair cosmetic compositionaccording to claim 3 wherein the silicone-containing copolymer comprisesfrom 5% to 92% by weight monomer A, from 7.5% to 80% by weight monomerB, and from 0.1% to 50% monomer C.
 5. A liquid hair cosmetic compositionaccording to claim 4 wherein monomer A is selected from acrylic acidesters of C₁ -C₁₈ alcohols, methacrylic acid esters of C₁ -C₁₈ alcohols,styrene, polystyrene macromer, vinyl acetate, vinyl chloride, vinylpropionate, vinylidene chloride, alpha-methylstyrene, t-butylstyrene,butadiene, cyclohexadiene, ethylene propylene, vinyl toluene, andmixtures thereof.
 6. A liquid hair cosmetic composition according toclaim 5 wherein monomer B is selected from acrylic acid, methacrylicacid, maleic acid, maleic anhydride, half esters of maleic anhydride,crotonic acid, itaconic acid and mixtures thereof.
 7. A liquid haircosmetic composition according to claim 6 wherein the siliconecontaining macromer has the general formula (II) in which p=0 and q=3, mis 1, R⁴ is alkyl, R¹ is hydrogen and R² is methyl.
 8. A liquid haircosmetic composition according to claim 7 wherein thesilicone-containing copolymer is selected from:acrylicacid/n-butylmethacrylate/polydimethylsiloxane (PDMS) macromer--20,000molecular weight (mw) (10/70/20); acrylic acid/isobutylmethacrylate,PDMS macromer--20,000 mw (20/60/20); acrylic acid/PDMSmacromer--20,000 mw (80/20 w/w) t-butylacrylate (tBA)/acrylic acid(AA)/PDMS macromer--10,000 mw (60/20/20) acrylic acid/isobutylmethacrylate/PDMS macromer--20,000 mw (10/70/20); acrylic acid/methylmethacrylate/PDMS macromer--20,000 mw (40/40/20); acrylic acid/isopropylmethacrylate/PDMS macromer--20,000 mw (25/65/15); acrylicacid/methoxyethyl methacrylate/PDMS macromer--20,000 mw (60/25/15);andmixtures thereof.
 9. A liquid hair cosmetic composition according toclaim 8 wherein the silicone-containing copolymer is neutralised to alevel of from about 40% to about 90% with sodium hydroxide.
 10. A liquidhair cosmetic composition according to claim 9 containing less than 0.7%by weight water.
 11. A liquid hair cosmetic product comprising ahairspray composition and spray dispenser means for containing andspraying the hairspray composition, and wherein the hairspraycomposition comprises:a) from about 0.1% by weight to about 10% byweight (acid basis) of a silicone-containing polycarboxylic acid hairstyling copolymer having a vinyl polymeric backbone, and having graftedto the backbone a silicone-contaning macromer having a weight averagemolecular weight of from about 1,000 to about 50,000; b) a neutralisingsystem consisting essentially of sodium hydroxide present at a levelsufficient to neutralise at least about 25% of the acid groups on thesilicone-contaning copolymer; c) from 0% to about 1% by weight of water;and d) a carrier suitable for application to hair wherein the carriercomprises an organic solvent for the silicone-containing copolymerconsisting essentially of C₁ -C₆ alkanols, C₁ -C₆ ethers, carbitol,acetone, or a mixture thereof.
 12. A liquid hair cosmetic compositionaccording to claim 3 wherein the silicone-containing macromer (C) has aweight average molecular weight of from about 50,000 to about 40,000.13. A liquid hair cosmetic composition according to claim 5 whereinmonomer A is selected from n-butylmethacrylate, isobutylmethacrylate,2-ethylhexylmethacrylate, methylmethacrylate, t-butylacrylate,t-butylmethacrylate, and mixtures thereof.
 14. A liquid hair cosmeticcomposition according to claim 6 wherein monomer B is selected fromacrylic acid and methacrylic acid and mixtures thereof.
 15. A liquidhair cosmetic composition according to claim 9 wherein the level is fromabout 55% to about 85%.
 16. A liquid hair cosmetic composition accordingto claim 15 wherein the level is from about 65% to about 80%.
 17. Aliquid hair cosmetic composition comprising:a) from about 0.1% by weightto about 10% by weight (acid basis) of a silicone-containingpolycarboxylic acid hair styling copolymer having a vinyl polymericbackbone, and having grafted to the backbone a silicone-containingmacromer having a weight average moleclar weight of from about 1,000 toabout 50,000; b) a neutralising system consisting essentially of sodiumhydroxide present at a level sufficient to neutralise at least about 25%of the acid groups on the silicone-containing copolymer; and c) acarrier suitable for application to hair wherein the carrier comprisesan organic solvent for the siliconecontainig copolymer consistingessentially of C₁ -C₆ alkanols, C₁ -C₆ ethers, carbitol, actone, or amixture thereof;wherein the composition is essentially free of water.